Azo dyes containing a diphenylurea nucleus



Patented Aug. 3, 1926.

1,594,sos

UNITED sTaiTes PATENT 'UOFFICE.

nanny alumina, or namnons mn'w- YORK; nssrenon. T NATIONAL ANILINE & cnnmrcan 00., meg, on NEW'YORK. n. Y., A CORPORATION on NEW YORK.

Brewing.

This invention relates to the manuf lifcture and production of new azo dyes containing,

; a diphenylurea nucleus which are o i value For dyeing cotton. The fabric, or other material, dyed with a dyestufi of-th'e present intention also constitutes a part of the ini vention.

i The new dyestutl' can be obtained by treating with phosgene in the presence of a substance adapted to absorb hydrochloric acid, a mixture of one or of two molecular proportions of a para-aminobenzene-a-zo-arylu o u d sulfomc or carboxyhc acid WlllCll contains only one ireeamino group, and whichjcorresponds with the general formula wherein R signifies an aryl nucleus of the fit benzene series which may contain substitu- 20 cuts and R a sulfonated or carboxylated aryl nucleus of the benzene or naphthalene series which may contain substituents, with one molecular proportion of a disazo dye- .aufi" which corresponds with. the general formula En on -l emu wherein R signifies an aryl nucleus of the benzene series which may contain substituents, R an aryl nucleus of the benzene series, 00 an integer having the value of 1 or 2, and Y a hydrogen atom or an amine or substitutedarnino group, or a substituentother than a nitro or a hydroxyl group, attached to the benzene nucleus. When Y is an amino group two molecular proportions Application filed li ovember'fi, 1925. Serial No. 67,432.

soluble in Water giving green solutions, and yield upon reduction with stannous chloride and hydrochloric acid a triaininonaphthol sulfonic acid, a diaminodiphenylurea, and a sulfonated or carboxylated aryl mona1nine of the benzene or naphthalene series. They dye cotton green shades which can be readily discharged by the action of discharging agents such, as for example, sodium hydrosulfite.

The following specific examples .will further illustrate the invention, but it is under stood that the invention is not limited thereto. The parts are by weight.

Example 1.-5 8.6 partsof the sodium salt of p-aminobenzene'azo-3fi-disulfo-1-amiho- 8-nap hol-azo-benzene (obtained for instance by couplingone molecular proportion of diazotized para-nitraniline into one molecular proportion of 1.8-aminonaphthol-3.6-disulfonic acid in acid solution and then combining the monazo compound thus pro-- paredwith one molecular proportion of diazotiz'ed aniline in alkaline solution and reducing the disazo dye thus produced with sodium sulfide) and 27.9 parts of the sodium salt of para-aminobenzene-azo-sal icylic acid (prepared for example by comining one molecular, proportion of diazotized p-nitraniline with one molecular proportion of salicylic id in alkaline solution and subsequently reducing the momzo dye thus produced with SOdlllIIl sulfiee) are dissolved in about 900 parts hot water containing about 10 parts of sodium carbonate, and the solution at a temperature of about to 60 C. is treated with phosgene until the formation of the urea is complete. During phosgenation the solution is maintained slightly alkaline by the addition of sodium carbonate at frequent intervals. The phosgenation is complete when a test portion acidulated with hydrochloric acid and treated with a little sodium nitrite gives no blue colorationwhen spotted on filter paper with a solution of sodium carbonate. When the formation ofthe urea is complete, the solution is cooled to about 30 C. and thedyestulf salted out by the addition of common produces a blue precipitate.

g2 1,594 see salt (about 90 parts) and the dyestufi' tiltered ofi', pressed and dried.

The new dyestulf thus obtained, in the and in the dry and pulverized state is a dark powder soluble in Water with a green color, soluble in concentrated sulfuric acid with a brown color Which on dilution with ice Upon reduction with stannous chloride and hydrochloric acid it yields aniline, amino-salicylic acid, 12.? triamino 8r naphthol 3.6 disullonic acid and p.p-diamino-diphenylurca. From a neutral or alkaline bath, it dyes cotton green tints of excellent 'tastness to light and washing which can be readily discharged.

Enudmple -6 O.l 1'iarts of the sodium salt of paraaminolaenzen'c-azo-ftfi-d isul to-l amino'naphthol-azo (p) aminobenzcnc (obtained for instance by coupling two molecular proportions of diazotized para-nitranilinc into one molecular proportion of 1.8-aminonaphthol-3.6-disulfonic acid, the first molecular proportion being coupled in acid soluu e one some --n==n -=o 00m nu -c ou N-i 1 on form of its sodium salt, most probably corresponds with the following formula:

HsN OH tion and the second in alkaline solution, and reducing with sodium sulfide the dis-Lino d e thus produced) and 55.8 parts of the sodium salt of para-amino-benzene-a'zo-salicylic acid are dissolved in about l000--1:200 parts dyestull' salted by the addition oi common salt and then filtered oli', pressed and dried.

The dyestutl' thus obtained, in the form of its sodium salt, is probably a composite product the major portion 01" which corrcspends with the following form did OOONe in which l.8-amino-naphthol-3.G-disul' onic acid is the middle component as illustrated in the above examples, other dis-azo compounds containing a LS-aminonaphthol monoor disulfonic acid as middle component may he used such as, for example, those obtainable by coupling on the one hand in acid solution the diazo compound of: nitrotoluidine, nitrocresidine, or Illl.l()(illl(liilmin( anisol, etc., with LS-aniinonaphthol dG-dh sulfonic acid or 1.8-a1ninonaphtholdatl-disule ionic acid or 1.8-aminoneplithol--sulfonic acid, etc., and then combining on the otl'c-r lumd in alkaline solution the monazo dye thus obtained with the 'diazo oom'polind of aniline or its 'liomologueis or suhsleiliutiorr products such are, nitramliine, toluidine; oliloi aniline, eulfanilio acid, anthmriilio acid,

".eto; and finally reduoiuglhe disazo com-- pound thus produoed with sodium sulfide. And instead of using the paIH-lIIllI10lJ(-)ll-' above exzunples,the1'e unny be employed other ammoaz o compounds wluoh conta n only one free amino group and which may be 'derlvd by coupling, for example, a diezo oleus.,whioli dyestuii? ill Elle driedond pulsulffouic or 'carboxylic acid of the benzene orv naphthalene Series which may or may not J contain substituente into a mono-amino of lbe benzene series, e. g., aniline, .oand mtoluidine, Xylidine, oresidino; onisidine, eloi I claim: 1. As 21 new dyeslufi u diplionylm'ee containing a pora amiuolieuzenoozo l.8-nminonoplithol-azoJonzene substance having; a

sulforiio acid group in khe naphthalene nuverized state and in the shave of moi alkali metal salt; is a dark powder soluble in Water,

yielding upon reduction with stannous chloride arid hydrochloric acid a lriamiuo-ll mphtliol sulfonic acid, a dimniuodiplieuylr urea and an aryl lllOIlilIIllllG derivative, and

which dyes cotton green shades which euu be readily discharged lay-the action of diselmrgiug' agents. y l

ii :neW dyestuli, the urlsylmuoluricml di xonylurezi of pare-mninobenzene-e220 sali oylio' acid on the one hand and p-omiuolierr- :zaeuoazo -3.6-disulfo-1.8-aminonaphtlrol 41m benzene on. the other l1a11d,'Which dyostud constitutes a black .p'owde' soluble in water giving a greensolufion, soluble in oonceu lrated sulfonic acid giving or brown solution, and yielding on reduction with stannous chloride and hydrochloric acid 1.2.7 -lzriamino-8- mphthol-3.6-disulfonic acid, p.p-dizmiiirodiphenylurea, aniline, and pam uminosali fllli 

